Disazo compounds having a further unsubstituted or substituted sulfophenyl diazo component radical and a 4-alkoxy- or arylsulfonyloxy benzene coupling component radical having an acylamina substituent

ABSTRACT

Disazo compounds of the formula ##STR1## in which A is a diazo component radical, 
     B is a coupling/diazo component radical of the 1,4-phenylene, 1,4-naphthylene or 5,6,7,8-tetrahydro-1,4-naphthylene series, 
     R 3  is hydrogen (C 1-4 )alkyl or ##STR2##   wherein ring Z is unsubstituted or monosubstituted by halo, (C 1-4 )alkyl or (C 1-4 )alkoxy, and 
     R 4  is (C 1-6 )alkyl, (C 1-6 )alkoxy, amino mono(C 1-6 )alkylamino or di(C 1-6 ) alkylamino, 
     with the proviso that the compound contains a single sulpho group on the diazo component radical A and no other water-solubilizing group, which compound is in free acid or salt form, and mixtures of such compounds which are useful as anionic dyestuffs for dyeing and printing substrates such as natural and synthetic polyamides (e.g., wool, silk and nylon), leather, polyurethanes and polyolefins modified to contain basic groups. The dyes may be used as such or in the form of liquid (e.g., concentrated aqueous) or solid preparations.

This application is a continuation-in-part of application Ser. No. 884,412, filed Mar. 8, 1978 and now abandoned.

The present invention relates to anionic disazo compounds, their preparation and use as anionic dyes.

More particularly, the present invention provides compounds of formula I, ##STR3## in which A is a diazo component radical,

B is a coupling/diazo component radical of the 1,4-phenylene, 1,4-naphthylene or 5,6,7,8-tetrahydro-1,4-naphthylene series,

R₃ is hydrogen, (C₁₋₄)alkyl or ##STR4## wherein ring Z is unsubstituted or monosubstituted by halogen, (C₁₋₄)alkyl or (C₁₋₄)alkoxy (R₃ is preferably other than hydrogen) and

R₄ is (C₁₋₆)alkyl, (C₁₋₆)alkoxy, amino, mono(C₁₋₆)alkylamino or di(C₁₋₆)alkylamino,

with the proviso that the compounds contain a single water-solubilizing group, which group is a sulpho group and is present on the diazo component radical A, which compounds are in free acid or salt form, and mixtures of compounds of formula I.

Preferably, the diazo component radical A is a diazo component radical of the benzene series.

Preferred compounds of formula I are those of formula Ia, ##STR5## in which B₁ is a radical of formula (a), (b) or (c) ##STR6## wherein each of R₁ and R₂, independently, is hydrogen, (C₁₋₄)alkyl, (C₁₋₄)alkoxy or monohalogen-substituted(C₁₋₄)alkyl,

R₅ is hydrogen, halogen, (C₁₋₄)alkyl, monohalogen-substituted(C₁₋₄)alkyl, (C₁₋₄)alkoxy, mono(C₁₋₆)alkylamino, di(C₁₋₆)alkylamino, alkyl(C₁₋₆)carbonylamino or alkoxy(C₁₋₆)carbonylamino,

R₆ is hydrogen, halogen, (C₁₋₄)alkyl or (C₁₋₄)alkoxy,

R₇ is hydrogen or methoxy,

M is hydrogen or an equivalent of a nonchromophoric cation, and

R₃ and R₄ are as defined above.

By halogen as used herein is meant fluorine, chlorine or bromine.

Any halogen as R₅ and/or R₆ is preferably chlorine or bromine, with chlorine being especially preferred.

Any halogen-substituted alkyl as R₅ is preferably a fluorosubstituted or chlorosubstituted alkyl, with chlorosubstituted alkyl being especially preferred. Any unsubstituted or substituted alkyl as R₅ preferably contains 1 or 2 carbon atoms, more preferably 1 carbon atom. Preferably, any alkyl as R₅ is unsubstituted.

Any alkyl as R₆ is preferably methyl or ethyl, with methyl being most preferred. Any alkoxy as R₅ and/or R₆ is peferably methoxy or ethoxy. Any monoalkylamino group as R₅ is preferably methylamino or ethylamino, more preferably methylamino. Any dialkylamino as R₅ preferably contains methyl and/or ethyl groups, more preferably methyl groups. The most preferred alkyl(C₁₋₆)carbonylamino as R₅ is acetylamino. Any alkoxy(C₁₋₆)carbonylamino as R₅ is preferably methoxy- or ethoxy-carbonylamino.

R₅ is preferably R₅ ', where R₅ ' is hydrogen, halogen, (C₁₋₄)alkyl, (C₁₋₄)alkoxy or acetylamino. More preferably, R₅ is R₅ ", where R₅ " is hydrogen, chlorine, (C₁₋₂)alkyl, (C₁₋₂)alkoxy or acetylamino. Even more preferably, R₅ is R₅ "', where R₅ "' is hydrogen, chlorine, methyl, methoxy or acetylamino, with hydrogen being most preferred.

R₆ is preferably R₆ ', where R₆ ' is hydrogen, halogen, (C₁₋₂)alkyl or (C₁₋₂)alkoxy. More preferably, R₆ is R₆ ", where R₆ " is hydrogen, chlorine or methyl, with hydrogen being especially preferred. Preferably, when R₅, R₅ ', R₅ " or R₅ "' signifies acetylamino, R₆ is hydrogen.

When R₅ and R₆ are both hydrogen, the sulpho group on ring A₁ is preferably in the 3- or 4-position. When one of R₅ and R₆ is hydrogen and the other is other than hydrogen, the two substituents on ring A₁ are preferably in the 2,4-, 2,5- or 3,4-positions, more preferably in the 2,4- or 2,5-positions, with the sulpho group preferably being in the 2-position when the other substituent is acetylamino. When both of R₅ and R₆ are other than hydrogen, the three substituents on ring A₁ are preferably in the 2,3,5-, 2,4,5- or 2,4,6-positions, with the 2,4,5- and 2,4,6-positions being more preferred and the sulpho group preferably being ortho or para to the azo group, especially methyl, ethyl, phenylsulphonyl or tosyl.

Any halogen-substituted alkyl as R₁ and/or R₂ is preferably a chlorosubstituted alkyl. Any unsubstituted alkyl or alkoxy or substituted alkyl as R₁ and/or R₂ preferably contains 1 or 2 carbon atoms, more preferably 1 carbon atom. Preferably any alkyl as R₁ and/or R₂ is unsubstituted.

R₁ is preferably R₁ ', where R₁ ' is hydrogen, methyl or methoxy; with methoxy being especially preferred.

R₂ is preferably R₂ ', where R₂ ' is hydrogen, methyl or methoxy. More preferably, R₂ is R₂ ", where R₂ " is methyl or methoxy.

R₇ is preferably hydrogen.

B or B₁ is preferably a radical of formula (a) or (b), in which latter radical R₇ is, as indicated above, preferably hydrogen. More preferably, B₁ is a radical of formula (a).

Any alkyl radical as R₃ is preferably methyl or ethyl. When R₃ is ##STR7## any halogen on ring Z is preferably chlorine; any alkyl on ring Z is preferably methyl or ethyl (especially methyl); and any alkoxy on ring Z is preferably methoxy or ethoxy.

R₃ is preferably R₃ ', where R₃ ' is hydrogen, methyl, ethyl, phenylsulphonyl or tosyl. More preferably, R₃ is R₃ ", where R₃ " is methyl or ethyl.

Any alkyl group as R₄ or as a substituent on an amino group as R₄ preferably contains 1 to 4 carbon atoms, more preferably 1 or 2 carbon atoms, with methyl being most preferred. Any alkoxy as R₄ preferably contains 1 to 4 carbon atoms, with methoxy and ethoxy being most preferred.

Preferably, R₄ is R₄ ', where R₄ ' is (C₁₋₄)alkyl, (C₁₋₄)alkoxy or unsubstituted amino. More preferably, R₄ is R₄ ", where R₄ " is methyl, ethyl, methoxy, ethoxy or amino. Even more preferably, R₄ is R₄ "', where R₄ "' is methyl, methoxy, ethoxy or amino. Most preferably, R₄ is R₄ ^(iv), where R₄ ^(iv) is methyl or amino, especially methyl.

The cation of the sulpho group in the compounds of formula I and the non-chromophoric cation M of the compounds of formula Ia may be any conventional cation for anionic dyestuffs. Examples of such cations are alkali metal cations such as sodium, lithium and potassium, and unsubstituted and substituted ammonium cations of the formula N.sup.⊕ (R₉)₄, where each R₉, independently, is hydrogen, (C₁₋₄)alkyl or 2-, 3- or 4-hydroxy(C₂₋₄)alkyl, with the proviso that at least one R₉ is other than hydroxyalkyl. Examples of such ammonium cations are ammonium, mono-, di-, tri- and tetra-methylammonium, triethylammonium and mono-, di- and tri-ethanolammonium.

Further preferred compounds according to the invention are those of formula Ia wherein

(i) B₁ is a radical of formula (a) or (b), R₅ is R₅ ', R₆ is R₆ ', R₇ is hydrogen, R₁ is R₁ ' and R₂ is R₂ ', especially those where the sulpho group on ring A₁ and any substituents as R₅ ' and/or R₆ ' are in the above-indicated preferred positions.

(ii) B₁ is a radical of formula (a) and all other variables are as given under (i).

(iii) B₁ is a radical of formula (a), R₅ is R₅ ', R₆ is R₆ ', R₁ is R₁ ', R₂ is R₂ ', R₃ is R₃ ' and R₄ is R₄ ', especially those where the sulpho group on ring A₁ and any substituents as R₅ ' and/or R₆ ' are in the above-indicated preferred positions.

(iv) B₁ is a radical of formula (a), R₅ is R₅ ", R₆ is R₆ ", with the proviso that when R₅ " is acetylamino, R₆ " is hydrogen, R₁ is methoxy, R₂ is R₂ ', R₃ is R₃ ' and R₄ is R₄ ", especially those where the sulpho group on ring A₁ and any substituents as R₅ " and/or R₆ " are in the above-indicated preferred positions.

(v) B₁ is a radical of formula (a), R₅ is R₅ "', R₆ is R₆ ", with the proviso that when R₅ "' is acetylamino, R₆ " is hydrogen, R₁ is methoxy, R₂ is R₂ ", R₃ is R₃ ' and R₄ is R₄ ", especially those where the sulpho group on ring A₁ and any substituents as R₅ "' and/or R₆ " are in the above-indicated preferred positions.

(vi) All variables are as defined in (v) with the exception that R₃ is R₃ ".

(vii) All variables are as defined in (v) with the exception that R₃ is R₃ " and R₄ is R₄ "'.

(viii) All variables are as defined in (v) with the exception that R₃ is R₃ " and R₄ is R₄ ^(iv).

(ix) All variables are as defined in (v) with the exception that R₃ is R₃ ", R₄ is methyl and both of R₅ and R₆ are hydrogen.

The present invention also provides a process for the production of compounds of formula I and mixtures thereof comprising

(a) coupling the diazotized amine of formula II,

    A--N═N--B--NH.sub.2                                    II

or a mixture thereof, with a phenol of formula III, ##STR8## or a mixture thereof, under alkaline conditions, to produce a compound of formula Ix, ##STR9## or a mixture thereof,

(b) etherifying or acylating a compound of formula Ix, or a mixture thereof, to form a compound of formula I wherein R₃ is other than hydrogen.

The coupling reaction in process variant (a) may be effected in accordance with known methods. Diazotization to produce the starting materials thereof may also be carried out in conventional manner.

The etherification or acylation of process variant (b) may be effected in known manner. Suitably, the etherification is carried out employing the corresponding dialkylsulphate. The reaction is suitably carried out in aqueous alkaline medium, the preferred pH being from 9 to 10. The reaction temperature is suitably from 30° to 90° C., more preferably from 60° to 80° C.

Acylation is suitably effected employing the corresponding sulphonylchloride. The reaction mixture is suitably aqueous which is made alkaline with soda, the preferred pH being from 8 to 10. The reaction temperature is suitably between 30° and 90° C., preferably between 60° and 70° C.

The compounds of formula I obtained may be isolated in accordance with conventional methods.

In general, as a result of the reaction conditions, compounds of formula I are obtained which are in salt form, which compounds may be converted into free acid form by known methods.

The compounds of formulae II and III are either known or may be prepared in accordance with known methods from readily available starting materials; for example, compounds of formula II may be obtained by coupling the diazonium compound of an amine A--NH₂, in acid medium, to an amine B--NH₂.

The compounds of formula I and mixtures thereof are useful for dyeing or printing anionic dyeable substrates. Suitable substrates include natural and synthetic polyamides, leather and basic-modified polyolefins and polyurethanes. Especially suitable are textile substrates consisting of or comprising natural and synthetic polyamides, such as wool and silk, and particularly nylon. The dyestuffs may advantageously be used for carpet printing.

The compounds of formula I, and mixtures thereof, may be employed as such or may be used in the form of liquid or solid preparations. The preparation of stable liquid, for example concentrated aqueous preparations, and solid preparations may be carried out in accordance with conventional methods, for example by dissolving in suitable solvents, optionally with the addition of conventional additives such as solubilizing agents, for example urea, or by grinding or granulating. Such preparations may be obtained in accordance with the procedure described in French Pat. Nos. 1,572,030 and 1,581,900.

Further, the compounds of formula I, and mixtures thereof, may be made up into preparations which are dispersible in cold water. Such dispersions may be prepared, for example, by grinding the dye wet or dry in the presence of one or more conventional anionic dispersing agents and optionally in the presence of other conventional additives, with subsequent spray-drying. The preparations so obtained are finely dispersed in cold water and are thus easy to handle.

Dyeing may be carried out in accordance with known methods, for example pad dyeing or exhaust dyeing, especially the latter as the compounds of formula I and mixtures thereof build-up from a neutral dyebath. Furthermore, the compounds of formula I and mixtures thereof are also useful for use in the "space-dyeing" process.

The compounds of formula I and mixtures thereof are well soluble in water, build-up well, migrate well and give even dyeings, especially on stripy nylon. The dyeings obtained possess notable light-fastness. Furthermore, the compounds of formula I and their mixtures give dyeings which have notable general fastness, such as wet-fastness, especially wash-, water-, milling- and sweat-fastness.

The compounds of formula I and mixtures thereof are suitable for combining with other dyes having neutral build-up, whereby dyeings having the above-mentioned advantageous properties are obtained. Further, such dyeings do not exhibit catalytic fading.

The following Examples further serve to illustrate the invention. In the Examples, all parts are by weight and all degrees are in degrees Centigrade.

EXAMPLE 1

33.7 Parts of the azo dye obtained by diazotizing 1-aminobenzene-4-sulphonic acid followed by coupling under acid conditions with 1-amino-2,5-dimethoxybenzene are dissolved with heating in 200 parts water and 12.5 parts of an approximately 25% ammonia solution and are then mixed with 6.9 parts sodium nitrite dissolved in 25 parts water. The nitrite-containing aminoazo dyestuff solution is added dropwise, over the period of 30 minutes, to a reaction vessel containing 28 parts of 30% hydrochloric acid, 40 parts water and 50 parts ice. After stirring for 1 hour, 2.76 parts sodium nitrite dissolved in 10 parts water and 11.5 parts 30% hydrochloric acid are added thereto and the solution is stirred for 18 hours, after which time diazotization is complete.

15.1 Parts 3-acetylamino-1-hydroxybenzene are stirred in 100 parts water with 1 part sodium carbonate at a pH of 9.5. The diazonium solution obtained as described above is added dropwise thereto from a compression pump over the period of 30 minutes, the pH of the solution being maintained at 9.5 by the addition of 27 parts sodium carbonate. After a further 15 minutes the coupling is complete. The precipitated dyestuff is isolated by filtering. The filtercake is dissolved at 80° (pH 9.5) with water to a volume of 750 parts by volume and mixed over a period of 30 minutes with 120 parts diethylsulphate, During the 30 minutes the pH is maintained at 9.5 by the dropwise addition of a 30% sodium hydroxide solution and the temperature is held at 80°, after which time the etherification is complete. The precipitated dyestuff which is isolated by filtration followed by drying is a brown powder and corresponds to the formula ##STR10## The dyestuff, which gives a red colour when dissolved in hot water, gives even dyeings on wool, silk and synthetic polyamides of brilliant yellowish-red shades which have good light- and wet-fastness. The dyestuff also has good build-up from a neutral bath.

In Table 1, further dyestuffs of the formula ##STR11## which are obtained in analogy with the procedure described in Example 1 are given. The significances for D, R₁, R₂, R₃ and R₄ are indicated in the respective columns, the position of the --NHCOR₄ group is indicated in the following column and the dye-shade on polyamide is indicated in column J, wherein a signifies orange, b signifies scarlet red, c signifies yellowish-red, d signifies brownish-red and e signifies yellowish-orange.

                                      TABLE 1                                      __________________________________________________________________________     Example                            Position of                                 No.  D            R.sub.1                                                                            R.sub.2                                                                            R.sub.3                                                                             R.sub.4                                                                            NHCOR.sub.4 group                                                                       J                                  __________________________________________________________________________     2    4-sulphophenyl                                                                              OCH.sub.3                                                                          OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH.sub.3                                                                           2        c                                  3    "            "   CH.sub.3                                                                           "    "   2        a                                  4    "            "   "   "    "   3        a                                  5    "            "   OCH.sub.3                                                                          CH.sub.3                                                                            "   3        c                                  6    "            "   H   C.sub.2 H.sub.5                                                                     "   3        c                                  7    "            H   H   "    "   3        a                                  8    "            OCH.sub.3                                                                          H   H    "   2        c                                  9    "            "   OCH.sub.3                                                                          tosyl                                                                               "   3        b                                  10   "            "   "   phenyl-                                                                             "   3        b                                                            sulphonyl                                            11   "            "   "   C.sub.2 H.sub.5                                                                     NH.sub.2                                                                           3        b                                  12   "            CH.sub.3                                                                           CH.sub.3                                                                           "    CH.sub.3                                                                           3        a                                  13   3-sulphophenyl                                                                              OCH.sub.3                                                                          OCH.sub.3                                                                          "    "   3        c                                  14   "            "   "   "    "   2        b                                  15   "            "   CH.sub.3                                                                           CH.sub.3                                                                            "   3        a                                  16   "            "   OCH.sub.3                                                                          "    "   3        c                                  17   "            "   "   C.sub.2 H.sub.5                                                                     C.sub.2 H.sub.5                                                                    3        c                                  18   "            "   CH.sub.3                                                                           CH.sub.3                                                                            OCH.sub.3                                                                          2        a                                  19   "            CH.sub.3                                                                           "   H    CH.sub.3                                                                           3        a                                  20   "            H   H   C.sub.2 H.sub.5                                                                     "   3        a                                  21   "            OCH.sub.3                                                                          OCH.sub.3                                                                          "    NH.sub.2                                                                           3        c                                  22   4-acetylamino-2-sulpho-                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH.sub.3                                                                           3        d                                       phenyl                                                                    23   4-acetylamino-2-sulpho-                                                                     "   CH.sub.3                                                                           CH.sub.3                                                                            "   3        b                                       phenyl                                                                    24   5-acetylamino-2-sulpho-                                                                     "   "   "    "   3        a                                       phenyl                                                                    25   2-methyl-4-sulphophenyl                                                                     "   "   C.sub.2 H.sub.5                                                                     "   3        b                                  26   "            "   "   "    "   2        a                                  27   "            "   OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                                                   "   3        b                                  28   2-methyl-5-sulphophenyl                                                                     "   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     "   3        b                                  29   "            "   "   CH.sub.3                                                                            "   2        a                                  30   4-methyl-2-sulphophenyl                                                                     "   "   "    "   2        a                                  31   2-ethyl-4-sulphophenyl                                                                      CH.sub.3                                                                           "   "    "   2        a                                  32   2,4-dimethyl-6-sulpho-                                                                      OCH.sub.3                                                                          "   "    "   3        a                                       phenyl                                                                    33   2,4-dimethyl-6-sulpho-                                                                      "   "   "    "   2        e                                       phenyl                                                                    34   2,4-dimethyl-6-sulpho-                                                                      "   "   phenyl-                                                                             NH.sub.2                                                                           3        a                                       phenyl               sulphonyl                                            35   2-methoxy-5-sulphophenyl                                                                    "   "   CH.sub.3                                                                            CH.sub.3                                                                           3        b                                  36   "            "   "   "    "   2        a                                  37   "            "   OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                     OC.sub.2 H.sub.5                                                                   2        b                                  38   2-ethoxy-5-sulphophenyl                                                                     "   "   CH.sub.3                                                                            CH.sub.3                                                                           2        b                                  39   4-chloro-2-sulphophenyl                                                                     OCH.sub.3                                                                          OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                     CH.sub.3                                                                           3        b                                  40   "            "   "   "    "   2        b                                  41   "            CH.sub.3                                                                           CH.sub.3                                                                           "    NH.sub.2                                                                           3        a                                  42   "            OCH.sub.3                                                                          OCH.sub.3                                                                          tosyl                                                                               CH.sub.3                                                                           3        b                                  43   2-chloro-5-sulphophenyl                                                                     "   "   C.sub.2 H.sub.5                                                                     "   3        b                                  44   "            "   "   "    "   2        b                                  45   "            "   CH.sub.3                                                                           CH.sub.3                                                                            OCH.sub.3                                                                          2        a                                  46   "            "   "   "    CH.sub.3                                                                           3        a                                  47   5-chloro-4-methyl-2-                                                                        "   "   "    "   3        b                                       sulphophenyl                                                              48   5-chloro-4-methyl-2-                                                                        "   OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                     "   3        c                                       sulphophenyl                                                              49   2,5-dichloro-4-sulpho-                                                                      "   CH.sub.3                                                                           "    "   3        b                                       phenyl                                                                    50   2,5-dichloro-4-sulpho-                                                                      "   OCH.sub.3                                                                          "    "   3        b                                       phenyl                                                                    51   3-sulphophenyl                                                                              "   "   tosyl                                                                               "   3        c                                  52   2-methoxy-5-sulpho-                                                                         "   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     "   3        b                                       phenyl                                                                    __________________________________________________________________________

EXAMPLE 53

27.7 Parts of 4-amino-1,1'-azobenzene-4'-sulphonic acid are dissolved at 60° in 300 parts water at pH 9-10 by addition of a 30% sodium hydroxide solution and are then mixed with 6.9 parts sodium nitrite dissolved in 25 parts water. The nitrite-containing aminoazo dyestuff solution is added dropwise, over a period of 15 minutes, to a reaction vessel containing 35 parts 30% hydrochloric acid, 50 parts water and 150 parts ice, the reaction temperature being 0°-5°. After stirring for 1 hour the excess sodium nitrite is destroyed by adding amidosulphonic acid.

15.4 Parts 1-acetylamino-2-hydroxybenzene are dissolved in 120 parts water and 10 parts 30% sodium hydroxide solution. The diazonium solution obtained as described above is added dropwise thereto over the period of 30 minutes, the pH of the solution being maintained at 10 by the addition of 30% sodium hydroxide solution. After a further 1 hour stirring, the pH is adjusted to 7.5-8.0. The precipitated dyestuff is isolated by filtration and washed with 5% sodium chloride solution.

The obtained filtercake is dissolved at 40° in 600 parts water by adding 10 parts 30% sodium hydroxide solution and is then mixed with 63 parts dimethylsulphate over the period of 30 minutes. During the 30 minutes the pH is maintained at 10.5-11.0 by the dropwise addition of 55 parts 30% sodium hydroxide solution and the temperature is held at 40°, after which the etherification is complete. The precipitated dyestuff which is isolated by filtration followed by washing with 2.5% aqueous sodium chloride solution and drying corresponds to the formula ##STR12##

The dyestuff is a red powder which gives an orange colour when dissolved in water and gives dyeings on wool and synthetic polyamides of clear reddish-yellow shades which have good light and wet fastnesses.

In analogy with the procedure described in Example 53 employing the corresponding amount of diethylsulphate instead of 63 parts dimethylsulphate, the dyestuff of the formula ##STR13## is obtained which gives dyeings on wool and synthetic polyamides of reddish-yellow shades having good light and wet fastnesses.

In Table 2 further dyestuffs of the formula ##STR14## which are obtained in analogy with the procedure described in Example 1, are given. The significances of D, B₂, R₃ and R₄ are given, wherein (Y) as B₂ signifies 1,4-naphthylene and (Z) as B₂ signifies 5,6,7,8-tetrahydro-1,4-naphthylene. As in Table 1, the dye shade on polyamide is indicated in column J, wherein the letters a to e have the same meanings as given above.

The dyestuffs of Examples 1 and 53 and the dyestuffs of Tables 1 and 2, which are all in the sodium salt form, may, depending on the reaction and isolation conditions, be obtained in free acid form or in other salt forms, for example those salt forms indicated as significances for M in the description hereinbefore.

                                      TABLE 2                                      __________________________________________________________________________     Example                      Position of                                       No.  D           B.sub.2                                                                           R.sub.3                                                                             R.sub.4                                                                            NHCOR.sub.4 group                                                                       J                                        __________________________________________________________________________     54   4-sulphophenyl                                                                             (Y)                                                                               C.sub.2 H.sub.5                                                                     CH.sub.3                                                                           3        a                                        55   "           (X)                                                                               CH.sub.3                                                                            "   3        a                                        56   3-sulphophenyl                                                                             (Y)                                                                               C.sub.2 H.sub.5                                                                     "   3        a                                        57   "           (Y)                                                                               "    NH.sub.2                                                                           2        a                                        58   4-sulphophenyl                                                                             (Y)                                                                               phenyl                                                                              CH.sub.3                                                                           3        a                                                            sulphonyl                                                  59   4-acetylamino-2-sulpho-                                                                    (Y)                                                                               C.sub.2 H.sub.5                                                                     "   3        b                                             phenyl                                                                    60   2-chloro-5-sulpho-                                                                         (Y)                                                                               CH.sub.3                                                                            C.sub.2 H.sub.5                                                                    2        a                                             phenyl                                                                    61   2-chloro-5-sulpho-                                                                         (Y)                                                                               "    CH.sub.3                                                                           3        a                                             phenyl                                                                    62   4-sulphophenyl                                                                             (Z)                                                                               C.sub.2 H.sub.5                                                                     "   3        c                                        63   3-sulphophenyl                                                                             (Z)                                                                               H    "   2        c                                        __________________________________________________________________________

APPLICATION EXAMPLE A

100 Parts of pre-wetted synthetic polyamide, for example nylon 66, are entered at 40° into a dyebath consisting of 4000 parts of water, 10 parts of anhydrous sodium sulphate and 2 parts of the dyestuff from Example 1.

The dye liquor is heated over the course of 30 minutes to boiling temperature and kept at this temperature for 1 hour. 4 Parts of glacial acetic acid are then added thereto and dyeing is completed with heating for a further 30 minutes at boiling temperature. During dyeing, the water that evaporates is continuously replaced. The yellowish-red dyed nylon cloth is then removed from the liquor, rinsed with water and dried. Wool may also be dyed by the same process.

Dyeings may be made in the same manner using the dyestuffs of Examples 2-63 or mixtures of two or more of the dyestuffs of Examples 1 to 63.

The dyeings have notable wet- and light-fastness.

APPLICATION EXAMPLE B

Polyamide is printed with a printing paste containing:

30 parts dyestuff of Example 1

50 parts urea

50 parts solubilizing agent (e.g. thiodiethylene glycol)

290 parts water

500 parts suitable thickening agent (e.g. based on carob bean gum)

20 parts acid donating agent (e.g. ammonium tartrate)

60 parts thiourea

The printed textile goods are steamed for 40 minutes at 102° (saturated steam), rinsed cold, subsequently washed at 60° with a dilute solution of a conventional detergent and rinsed again with cold water. A yellowish red print having notable light-and wet-fastness is obtained.

In analogous manner printing pastes may be made employing the dyestuffs of Examples 2-63 or mixtures of two or more of the dyestuffs of Examples 1-63. Such pastes may be employed for printing in accordance with the above given procedure. 

What is claimed is:
 1. A compound of the formula ##STR15## or a mixture of such compounds, wherein each of R₁ ' and R₂ ' is independently hydrogen, methyl or methoxy,R₃ is methyl, ethyl, phenylsulfonyl or tosyl, R₄ is methyl, ethyl, methoxy, ethoxy or amino, R₅ is hydrogen, chloro, C₁₋₂ alkyl, C₁₋₂ alkoxy or acetamido, R₆ is hydrogen, chloro or methyl, with the proviso that R₆ is hydrogen when R₅ is acetamido, and M is hydrogen or a non-chromophoric cation.
 2. A compound according to claim 1, or a mixture of such compounds, wherein(i) when R₅ is hydrogen and R₆ is hydrogen, the --SO₃ M group is in the 3- or 4-position, (ii) when one of R₅ and R₆ is hydrogen and the other is other than hydrogen, the two substituents are in the 2,4- or 2,5-positions, and (iii) when both R₅ and R₆ are other than hydrogen, one of R₅, R₆ and the --SO₃ M group is in the 2-position, another is in the 4-position and the third is in the 5- or 6-position.
 3. A compound according to claim 1, or a mixture of such compounds,wherein R₆ is hydrogen.
 4. A compound according to claim 1, or a mixture of such compounds, wherein R₅ is hydrogen, chloro, methyl, methoxy or acetamido.
 5. A compound according to claim 1, or a mixture of such compounds, wherein R₃ is methyl or ethyl, and R₄ is methyl, methoxy, ethoxy or amino.
 6. A compound according to claim 1, or a mixture of such compounds, wherein R₄ is methyl or amino.
 7. A compound according to claim 5, or a mixture of such compounds, whereinR₅ is hydrogen, chloro, methyl, methoxy or acetamido, and R₆ is hydrogen.
 8. A compound according to claim 7, or a mixture of such compounds, wherein R₄ is methyl or amino.
 9. A compound according to claim 8, or a mixture of such compounds, wherein R₄ is methyl.
 10. A compound according to claim 7, or a mixture of such compounds, wherein R₅ is hydrogen.
 11. A compound according to claim 10, or a mixture of such compounds, wherein R₄ is methyl.
 12. The compound according to claim 11 having the formula ##STR16## or a salt thereof having a non-chromophoric cation.
 13. A compound according to claim 1, or a mixture of such compounds, whereinR₁ ' is methoxy, R₂ ' is methyl or methoxy, R₃ is methyl or ethyl, R₄ is methyl, methoxy, ethoxy or amino, R₅ is hydrogen, chloro, methyl, methoxy or acetamido, and R₆ is hydrogen, chloro or methyl, with the proviso that R₆ is hydrogen when R₅ is acetamido, and wherein(i) when R₅ is hydrogen and R₆ is hydrogen, the --SO₃ M group is in the 3- or 4-position, (ii) when one of R₅ and R₆ is hydrogen and the other is other than hydrogen, the two substituents are in the 2,4- or 2,5-positions, and (iii) when both R₅ and R₆ are other than hydrogen, one of R₅, R₆ and the --SO₃ M group is in the 2-position, another is in the 4-position and the third is in the 5- or 6-position.
 14. A compound according to claim 13, or a mixture of such compounds, wherein R₄ is methyl or amino.
 15. The compound according to claim 11 having the formula ##STR17## or a salt thereof having a non-chromophoric cation.
 16. The compound according to claim 11 having the formula ##STR18## or a salt thereof having a non-chromophoric cation. 